Kinetics and Mechanism of the Anilinolyses of O-Methyl, O-Propyl and O-Isopropyl Phenyl Phosphonochloridothioates in Acetonitrile

Title
Kinetics and Mechanism of the Anilinolyses of O-Methyl, O-Propyl and O-Isopropyl Phenyl Phosphonochloridothioates in Acetonitrile
Authors
이해황
Keywords
Thiophosphoryl transfer reaction, Anilinolysis, O-Methyl, O-propyl and O-isopropyl phenyl phosphonochloridothioates, Deuterium kinetic isotope effect
Issue Date
2013
Publisher
BULLETIN OF THE KOREAN CHEMICAL SOCIETY
Series/Report no.
BULLETIN OF THE KOREAN CHEMICAL SOCIETY ; Vol34 no.4 Startpage 1096 Endpage 1100
Abstract
The kinetic studies on the reactions of O-methyl (1), O-propyl (3) and O-isopropyl (4) phenyl phosphonochloridothioates with substituted anilines and deuterated anilines have been carried out in acetonitrile at 55.0 oC. A concerted SN2 mechanism is proposed for the anilinolyses of 1, 3 and 4. The anilinolysis rates of the phosphonochloridothioates are predominantly dependent upon the steric effects over the inductive effects of the two ligands. The deuterium kinetic isotope effects (DKIEs; kH/kD) are primary normal with 1 and 3, while secondary inverse with 4. Primary normal and secondary inverse DKIEs are rationalized by frontside and backside nucleophilic attack transition state, respectively. The DKIEs of the phosphonochloridothioates do not have any consistent correlations with the two ligands.
URI
http://dx.doi.org/10.5012/bkcs.2013.34.4.1096
http://dspace.inha.ac.kr/handle/10505/33107
ISSN
0253-2964
Appears in Collections:
College of Natural Science(자연과학대학) > Chemistry (화학) > Local Access Journal Papers, Reports(화학 논문, 보고서)

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